Polydiorganosiloxane polyoxamide copolymers

ABSTRACT

Polydiorganosiloxane polyoxamide, linear, block copolymers and methods of making the copolymers are provided. The method of making the copolymers involves reacting a diamine with a precursor having at least one polydiorganosiloxane segment and at least two oxalyamino groups. The polydiorganosiloxane polyoxamide block copolymers are of the (AB) n  type.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 14/471,354, filedAug. 28, 2014, now allowed, which is a continuation of U.S. Ser. No.14/058,953, filed Oct. 21, 2013, now issued as U.S. Pat. No. 8,853,323on Oct. 7, 2014, which is a continuation of Ser. No. 12/979,785, filedDec. 28, 2010, now issued as U.S. Pat. No. 8,586,668 on Nov. 19, 2013,which is a continuation of U.S. Ser. No. 12/362,155, filed Jan. 29,2009, now issued as U.S. Pat. No. 7,883,652 on Feb. 8, 2011, which is acontinuation of U.S. Ser. No. 11/317,271, filed Dec. 23, 2005, nowissued as U.S. Pat. No. 7,501,184 on Mar. 10, 2009, the disclosure ofwhich is incorporated by referenced in its entirety herein.

TECHNICAL FIELD

Polydiorganosiloxane polyoxamide copolymers and methods of making thecopolymers are described.

BACKGROUND

Siloxane polymers have unique properties derived mainly from thephysical and chemical characteristics of the siloxane bond. Theseproperties include low glass transition temperature, thermal andoxidative stability, resistance to ultraviolet radiation, low surfaceenergy and hydrophobicity, high permeability to many gases, andbiocompatibility. The siloxane polymers, however, often lack tensilestrength.

The low tensile strength of the siloxane polymers can be improved byforming block copolymers. Some block copolymers contain a “soft”siloxane polymeric block or segment and any of a variety of “hard”blocks or segments. Polydiorganosiloxane polyamides andpolydiorganosiloxane polyureas are exemplary block copolymers.

Polydiorganosiloxane polyamides have been prepared by condensationreactions of amino terminated silicones with short-chained dicarboxylicacids. Alternatively, these copolymers have been prepared bycondensation reactions of carboxy terminated silicones withshort-chained diamines. Because polydiorganosiloxanes (e.g.,polydimethylsiloxanes) and polyamides often have significantly differentsolubility parameters, it can be difficult to find reaction conditionsfor production of siloxane-based polyamides that result in high degreesof polymerization, particularly with larger homologs of thepolyorganosiloxane segments. Many of the known siloxane-based polyamidecopolymers contain relatively short segments of the polydiorganosiloxane(e.g., polydimethylsiloxane) such as segments having no greater thanabout 30 diorganosiloxy (e.g., dimethylsiloxy) units or the amount ofthe polydiorganosiloxane segment in the copolymer is relatively low.That is, the fraction (i.e., amount based on weight) ofpolydiorganosiloxane (e.g., polydimethylsiloxane) soft segments in theresulting copolymers tends to be low.

Polydiorganosiloxane polyureas are another type of block copolymer.Although these block copolymers have many desirable characteristics,some of them tend to degrade when subjected to elevated temperaturessuch as 250° C. or higher.

SUMMARY

Polydiorganosiloxane polyoxamide block copolymers and methods of makingthe copolymers are provided. The methods of making the copolymersinvolve the use of a precursor that includes at least onepolydiorganosiloxane segment and at least two oxalylamino groups. Theresulting copolymers have a plurality of oxalylamino and aminoxalylaminogroups (e.g., the oxalylamino groups can be part of the aminoxalylaminogroups). The polydiorganosiloxane polyoxamide copolymers can contain arelatively large fraction of the polydiorganosiloxane segment comparedto many known polydiorganosiloxane polyamide copolymers. Thepolydiorganosiloxane polyoxamide copolymer can usually be subjected toelevated temperatures up to 250° C. or higher without apparentdegradation.

In a first aspect, a copolymeric material is provided that contains atleast two repeat units of Formula I.

In this formula, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo. EachY is independently an alkylene, aralkylene, or a combination thereof.Subscript n is independently an integer of 0 to 1500 and subscript p isan integer of 1 to 10. Group G is a divalent group that is the residueunit that is equal to a diamine of formula R³HN-G-NHR³ minus the two—NHR³ groups (i.e., amino groups). Group R³ is hydrogen or alkyl or R³taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group. Each asterisk indicates theposition of attachment of the repeating unit to another group such asanother repeat unit.

In a second aspect, a method of making a copolymeric material having atleast two repeat units of Formula I is provided. The method includesmixing together under reaction conditions

a) a precursor of Formula II; and

b) a diamine having two primary amino groups, two secondary aminogroups, or one primary amino group and one secondary amino group. Thediamine is of formula R³HN-G-NHR³ where G is a divalent group that isthe residue unit that is equal to a diamine of formula minus the two—NHR³ groups (i.e., amino groups). Group R³ is hydrogen or alkyl or R³taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group.

In Formula II, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo. EachR² is independently an alkyl, haloalkyl, aryl, or aryl substituted withan alkyl, alkoxy, halo, or alkoxycarbonyl. Each Y is independently analkylene, aralkylene, or a combination thereof. The subscript n isindependently an integer of 0 to 1500 and the subscript p is an integerof 1 to 10.

In a third aspect, articles are provided that contain a copolymer havingat least two repeat units of Formula I.

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which can be used invarious combinations. In each instance, the recited list serves only asa representative group and should not be interpreted as an exclusivelist.

DETAILED DESCRIPTION OF THE INVENTION

Polydiorganosiloxane polyoxamide block copolymers and methods of makingthe copolymers are provided. The polydiorganosiloxane polyoxamidecopolymers, which are of the (AB)_(n) type, are the condensationreaction product of (a) a diamine having primary or secondary aminogroups with (b) a precursor having at least one polydiorganosiloxanesegment and at least two oxalylamino groups. The copolymers have many ofthe desirable features of polysiloxanes such as low glass transitiontemperatures, thermal and oxidative stability, resistance to ultravioletradiation, low surface energy and hydrophobicity, and high permeabilityto many gases. Additionally, the copolymers can have improved mechanicalstrength and elastomeric properties compared to polysiloxanes. At leastsome of the copolymers are optically clear, have a low refractive index,or both.

DEFINITIONS

The terms “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

The term “alkenyl” refers to a monovalent group that is a radical of analkene, which is a hydrocarbon with at least one carbon-carbon doublebond. The alkenyl can be linear, branched, cyclic, or combinationsthereof and typically contains 2 to 20 carbon atoms. In someembodiments, the alkenyl contains 2 to 18, 2 to 12, 2 to 10, 4 to 10, 4to 8, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkenyl groupsinclude ethenyl, n-propenyl, and n-butenyl.

The term “alkyl” refers to a monovalent group that is a radical of analkane, which is a saturated hydrocarbon. The alkyl can be linear,branched, cyclic, or combinations thereof and typically has 1 to 20carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples ofalkyl groups include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl,n-heptyl, n-octyl, and ethylhexyl.

The term “alkylene” refers to a divalent group that is a radical of analkane. The alkylene can be straight-chained, branched, cyclic, orcombinations thereof. The alkylene often has 1 to 20 carbon atoms. Insome embodiments, the alkylene contains 1 to 18, 1 to 12, 1 to 10, 1 to8, 1 to 6, or 1 to 4 carbon atoms. The radical centers of the alkylenecan be on the same carbon atom (i.e., an alkylidene) or on differentcarbon atoms.

The term “alkoxy” refers to a monovalent group of formula —OR where R isan alkyl group.

The term “alkoxycarbonyl” refers to a monovalent group of formula—(CO)OR where R is an alkyl group and (CO) denotes a carbonyl group withthe carbon attached to the oxygen with a double bond.

The term “aralkyl” refers to a monovalent group of formula —R^(a)—Arwhere R^(a) is an alkylene and Ar is an aryl group. That is, the aralkylis an alkyl substituted with an aryl. The term “aralkylene” refers to adivalent group of formula —R^(a)—Ar^(a)— where R^(a) is an alkylene andAr^(a) is an arylene (i.e., an alkylene is bonded to an arylene).

The term “aryl” refers to a monovalent group that is aromatic andcarbocyclic. The aryl can have one to five rings that are connected toor fused to the aromatic ring. The other ring structures can bearomatic, non-aromatic, or combinations thereof. Examples of aryl groupsinclude, but are not limited to, phenyl, biphenyl, terphenyl, anthryl,naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl,pyrenyl, perylenyl, and fluorenyl.

The term “arylene” refers to a divalent group that is carbocyclic andaromatic. The group has one to five rings that are connected, fused, orcombinations thereof. The other rings can be aromatic, non-aromatic, orcombinations thereof. In some embodiments, the arylene group has up to 5rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromaticring. For example, the arylene group can be phenylene.

The term “aryloxy” refers to a monovalent group of formula —OAr where Aris an aryl group.

The term “carbonyl” refers to a divalent group of formula —(CO)— wherethe carbon atom is attached to the oxygen atom with a double bond.

The term “halo” refers to fluoro, chloro, bromo, or iodo.

The term “haloalkyl” refers to an alkyl having at least one hydrogenatom replaced with a halo. Some haloalkyl groups are fluoroalkyl groups,chloroalkyl groups, or bromoalkyl groups.

The term “heteroalkylene” refers to a divalent group that includes atleast two alkylene groups connected by a thio, oxy, or —NR— where R isalkyl. The heteroalkylene can be linear, branched, cyclic, orcombinations thereof and can include up to 60 carbon atoms and up to 15heteroatoms. In some embodiments, the heteroalkylene includes up to 50carbon atoms, up to 40 carbon atoms, up to 30 carbon atoms, up to 20carbon atoms, or up to 10 carbon atoms. Some heteroalkylenes arepolyalkylene oxides where the heteroatom is oxygen.

The term “oxalyl” refers to a divalent group of formula —(CO)—(CO)—where each (CO) denotes a carbonyl group.

The terms “oxalylamino” and “aminoxalyl” are used interchangeably torefer to a divalent group of formula —(CO)—(CO)—NH— where each (CO)denotes a carbonyl.

The term “aminoxalylamino” refers to a divalent group of formula—NH—(CO)—(CO)—NR^(d)— where each (CO) denotes a carbonyl group and R^(d)is hydrogen, alkyl, or part of a heterocyclic group along with thenitrogen to which they are both attached. In most embodiments, R^(d) ishydrogen or alkyl. In many embodiments, R^(d) is hydrogen.

The terms “polymer” and “polymeric material” refer to both materialsprepared from one monomer such as a homopolymer or to materials preparedfrom two or more monomers such as a copolymer, terpolymer, or the like.Likewise, the term “polymerize” refers to the process of making apolymeric material that can be a homopolymer, copolymer, terpolymer, orthe like. The terms “copolymer” and “copolymeric material” refer to apolymeric material prepared from at least two monomers.

The term “polydiorganosiloxane” refers to a divalent segment of formula

where each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof; andsubscript n is independently an integer of 0 to 1500.

The terms “room temperature” and “ambient temperature” are usedinterchangeably to mean temperatures in the range of 20° C. to 25° C.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numbers setforth are approximations that can vary depending upon the desiredproperties using the teachings disclosed herein.

Compounds and Compositions

A linear, polydiorganosiloxane polyoxamide block copolymer is providedthat contains at least two repeat units of Formula I.

In this formula, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo. EachY is independently an alkylene, aralkylene, or a combination thereof.Subscript n is independently an integer of 0 to 1500 and the subscript pis an integer of 1 to 10. Group G is a divalent group that is theresidue unit that is equal to a diamine of formula R³HN-G-NHR³ minus thetwo —NHR³ groups. Group R³ is hydrogen or alkyl (e.g., an alkyl having 1to 10, 1 to 6, or 1 to 4 carbon atoms) or R³ taken together with G andwith the nitrogen to which they are both attached forms a heterocyclicgroup (e.g., R³HN-G-NHR³ is piperazine or the like). Each asterisk (*)indicates a site of attachment of the repeat unit to another group inthe copolymer such as, for example, another repeat unit of Formula I.

Suitable alkyl groups for R¹ in Formula I typically have 1 to 10, 1 to6, or 1 to 4 carbon atoms. Exemplary alkyl groups include, but are notlimited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl.Suitable haloalkyl groups for R¹ often have only a portion of thehydrogen atoms of the corresponding alkyl group replaced with a halogen.Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groupswith 1 to 3 halo atoms and 3 to 10 carbon atoms. Suitable alkenyl groupsfor R¹ often have 2 to 10 carbon atoms. Exemplary alkenyl groups oftenhave 2 to 8, 2 to 6, or 2 to 4 carbon atoms such as ethenyl, n-propenyl,and n-butenyl. Suitable aryl groups for R¹ often have 6 to 12 carbonatoms. Phenyl is an exemplary aryl group. The aryl group can beunsubstituted or substituted with an alkyl (e.g., an alkyl having 1 to10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), an alkoxy(e.g., an alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). Suitablearalkyl groups for R¹ usually have an alkylene group with 1 to 10 carbonatoms and an aryl group with 6 to 12 carbon atoms. In some exemplaryaralkyl groups, the aryl group is phenyl and the alkylene group has 1 to10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms (i.e., thestructure of the aralkyl is alkylene-phenyl where an alkylene is bondedto a phenyl group).

In some repeat units of Formula I, at least 50 percent of the R¹ groupsare methyl. For example, at least 60 percent, at least 70 percent, atleast 80 percent, at least 90 percent, at least 95 percent, at least 98percent, or at least 99 percent of the R¹ groups can be methyl. Theremaining R¹ groups can be selected from an alkyl having at least twocarbon atoms, haloalkyl, aralkyl, alkenyl, aryl, or aryl substitutedwith an alkyl, alkoxy, or halo.

Each Y in Formula I is independently an alkylene, aralkylene, or acombination thereof. Suitable alkylene groups typically have up to 10carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4carbon atoms. Exemplary alkylene groups include methylene, ethylene,propylene, butylene, and the like. Suitable aralkylene groups usuallyhave an arylene group with 6 to 12 carbon atoms bonded to an alkylenegroup with 1 to 10 carbon atoms. In some exemplary aralkylene groups,the arylene portion is phenylene. That is, the divalent aralkylene groupis phenylene-alkylene where the phenylene is bonded to an alkylenehaving 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used hereinwith reference to group Y, “a combination thereof” refers to acombination of two or more groups selected from an alkylene andaralkylene group. A combination can be, for example, a single aralkylenebonded to a single alkylene (e.g., alkylene-arylene-alkylene). In oneexemplary alkylene-arylene-alkylene combination, the arylene isphenylene and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

Each subscript n in Formula I is independently an integer of 0 to 1500.For example, subscript n can be an integer up to 1000, up to 500, up to400, up to 300, up to 200, up to 100, up to 80, up to 60, up to 40, upto 20, or up to 10. The value of n is often at least 1, at least 2, atleast 3, at least 5, at least 10, at least 20, or at least 40. Forexample, subscript n can be in the range of 40 to 1500, 0 to 1000, 40 to1000, 0 to 500, 1 to 500, 40 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to100, 1 to 80, 1 to 40, or 1 to 20.

The subscript p is an integer of 1 to 10. For example, the value of p isoften an integer up to 9, up to 8, up to 7, up to 6, up to 5, up to 4,up to 3, or up to 2. The value of p can be in the range of 1 to 8, 1 to6, or 1 to 4.

Group G in Formula I is a residual unit that is equal to a diaminecompound of formula R³HN-G-NHR³ minus the two amino groups (i.e., —NHR³groups). The diamine can have primary or secondary amino groups. GroupR³ is hydrogen or alkyl (e.g., an alkyl having 1 to 10, 1 to 6, or 1 to4 carbon atoms) or R³ taken together with G and with the nitrogen towhich they are both attached forms a heterocyclic group (e.g.,R³HN-G-NHR³ is piperazine). In most embodiments, R³ is hydrogen or analkyl. In many embodiments, both of the amino groups of the diamine areprimary amino groups (i.e., both R³ groups are hydrogen) and the diamineis of formula H₂N-G-NH₂.

In some embodiments, G is an alkylene, heteroalkylene,polydiorganosiloxane, arylene, aralkylene, or a combination thereof.Suitable alkylenes often have 2 to 10, 2 to 6, or 2 to 4 carbon atoms.Exemplary alkylene groups include ethylene, propylene, butylene, and thelike. Suitable heteroalkylenes are often polyoxyalkylenes such aspolyoxyethylene having at least 2 ethylene units, polyoxypropylenehaving at least 2 propylene units, or copolymers thereof. Suitablepolydiorganosiloxanes include the polydiorganosiloxane diamines ofFormula III, which are described below, minus the two amino groups.Exemplary polydiorganosiloxanes include, but are not limited to,polydimethylsiloxanes with alkylene Y groups. Suitable aralkylene groupsusually contain an arylene group having 6 to 12 carbon atoms bonded toan alkylene group having 1 to 10 carbon atoms. Some exemplary aralkylenegroups are phenylene-alkylene where the phenylene is bonded to analkylene having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbonatoms, or 1 to 4 carbon atoms. As used herein with reference to group G,“a combination thereof” refers to a combination of two or more groupsselected from an alkylene, heteroalkylene, polydiorganosiloxane,arylene, and aralkylene. A combination can be, for example, anaralkylene bonded to an alkylene (e.g., alkylene-arylene-alkylene). Inone exemplary alkylene-arylene-alkylene combination, the arylene isphenylene and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

The polydiorganosiloxane polyoxamide tends to be free of groups having aformula —R^(a)—(CO)—NH— where R^(a) is an alkylene. All of thecarbonylamino groups along the backbone of the copolymeric material arepart of an oxalylamino group (i.e., the —(CO)—(CO)—NH— group). That is,any carbonyl group along the backbone of the copolymeric material isbonded to another carbonyl group and is part of an oxalyl group. Morespecifically, the polydiorganosiloxane polyoxamide has a plurality ofaminoxalylamino groups.

The polydiorganosiloxane polyoxamide is a linear, block copolymer andcan be an elastomeric material. Unlike many of the knownpolydiorganosiloxane polyamides that are generally formulated as brittlesolids or hard plastics, the polydiorganosiloxane polyoxamides can beformulated to include greater than 50 weight percentpolydiorganosiloxane segments based on the weight of the copolymer. Theweight percent of the diorganosiloxane in the polydiorganosiloxanepolyoxamides can be increased by using higher molecular weightpolydiorganosiloxanes segments to provide greater than 60 weightpercent, greater than 70 weight percent, greater than 80 weight percent,greater than 90 weight percent, greater than 95 weight percent, orgreater than 98 weight percent of the polydiorganosiloxane segments inthe polydiorganosiloxane polyoxamides. Higher amounts of thepolydiorganosiloxane can be used to prepare elastomeric materials withlower modulus while maintaining reasonable strength.

Some of the polydiorganosiloxane polyoxamides can be heated to atemperature up to 200° C., up to 225° C., up to 250° C., up to 275° C.,or up to 300° C. without noticeable degradation of the material. Forexample, when heated in a thermogravimetric analyzer in the presence ofair, the copolymers often have less than a 10 percent weight loss whenscanned at a rate 50° C. per minute in the range of 20° C. to about 350°C. Additionally, the copolymers can often be heated at a temperaturesuch as 250° C. for 1 hour in air without apparent degradation asdetermined by no detectable loss of mechanical strength upon cooling.

The copolymeric material of Formula I can be optically clear. As usedherein, the term “optically clear” refers to a material that is clear tothe human eye. An optically clear copolymeric material often has aluminous transmission of at least about 90 percent, a haze of less thanabout 2 percent, and opacity of less than about 1 percent in the 400 to700 nm wavelength range. Both the luminous transmission and the haze canbe determined using, for example, the method of ASTM-D 1003-95.

Additionally, the copolymeric material of Formula I can have a lowrefractive index. As used herein, the term “refractive index” refers tothe absolute refractive index of a material (e.g., copolymeric material)and is the ratio of the speed of electromagnetic radiation in free spaceto the speed of the electromagnetic radiation in the material ofinterest. The electromagnetic radiation is white light. The index ofrefraction is measured using an Abbe refractometer, availablecommercially, for example, from Fisher Instruments of Pittsburgh, Pa.The measurement of the refractive index can depend, to some extent, onthe particular refractometer used. The copolymeric material usually hasa refractive index in the range of about 1.41 to about 1.50.

Optionally, non-reactive additives such as fillers, pigments,stabilizers, antioxidants, flame retardants, compatibilizers, and thelike can be added to the copolymeric materials.

The polydiorganosilocane polyoxamides are soluble in many common organicsolvents such as, for example, toluene, tetrahydrofuran,dichloromethane, aliphatic hydrocarbons (e.g., alkanes such as hexane),or mixtures thereof.

The polydiorganosiloxane polyoxamides can be cast from solvents as film,molded or embossed in various shapes, or extruded into films. The hightemperature stability of the copolymeric material makes them well suitedfor extrusion methods of film formation. The films can be opticallyclear. A multilayer film containing the polydiorganosiloxane polyoxamideblock copolymers is further described in copending patent applicationwith Attorney Docket No. 61494US002 filed on the same day as the presentapplication, incorporated herein by reference in its entirety.

Various articles are provided that contain a polydiorganosiloxanepolyoxamide copolymer having at least two repeat units of Formula I. Thearticle, for example, can include a layer containing thepolydiorganosiloxane polyoxamide copolymer and one or more optionalsubstrates. For example, the polydiorganosiloxane polyoxamide copolymercan be in a layer adjacent to a first substrate or positioned between afirst substrate and a second substrate. That is, the article can bearranged in the following order: a first substrate, a layer containingthe polydiorganosiloxane polyoxamide copolymer, and a second substrate.As used herein, the term “adjacent” refers to a first layer thatcontacts a second layer or that is positioned in proximity to the secondlayer but separated from the second layer by one or more additionallayers.

The polydiorganosiloxane polyoxamides can be formulated into adhesivecompositions such as pressure sensitive adhesives and heat activatedadhesives that contain a tackifier. Such adhesive compositions arefurther described in copending patent application with Attorney DocketNo. 61371US002 filed on the same day as the present application,incorporated herein by reference in its entirety.

Additionally, the polydiorganosiloxane polyoxamides can be used as a hotmelt adhesive. Typically, the hot melt adhesive contains little or notackifier. The hot melt adhesives can be used, for example, to bond twosurfaces together into a composite. That is, the hot melt adhesive canbe used to bond a first substrate to a second substrate with the hotmelt adhesive positioned between the first and second substrates. Duringapplication to a surface such as the surface of a substrate, hot meltadhesives are desirably sufficiently fluid to wet the surface completelyand leave no voids, even if the surface is rough. Such an adhesivecomposition typically has a low viscosity at the time of application andthen sets into a solid upon cooling. The cohesive strength develops uponcooling. Alternatively, the hot melt adhesive composition can beformulated with a solvent or carrier that lowers the viscositysufficiently to permit wetting of the surface. The solvent or carriercan then be removed to provide a solid coating having cohesive strength.

Methods of Making Polydiorganosiloxane Polyoxamide Copolymers

The linear block copolymers having repeat units of Formula I can beprepared, for example, as represented in Reaction Scheme A.

In this reaction scheme, a precursor of Formula II is combined underreaction conditions with a diamine having two primary or secondary aminogroups, two secondary amino groups, or one primary amino group and onesecondary amino group. The diamine is usually of formula R³HN-G-NHR³.The R²OH by-product is typically removed from the resultingpolydiorganosiloxane polyoxamide.

The diamine R³HN-G-NHR³ in Reaction Scheme A has two amino groups (i.e.,—NHR³). Group R³ is hydrogen or alkyl (e.g., an alkyl having 1 to 10, 1to 6, or 1 to 4 carbon atoms) or R³ taken together with G and with thenitrogen to which they are both attached forms a heterocyclic group(e.g., the diamine is piperazine or the like). In most embodiments, R³is hydrogen or alkyl. In many embodiments, the diamine has two primaryamino groups (i.e., each R³ group is hydrogen) and the diamine is offormula H₂N-G-NH₂. The portion of the diamine exclusive of the two aminogroups is referred to as group G in Formula I.

The diamines are sometimes classified as organic diamines orpolydiorganosiloxane diamines with the organic diamines including, forexample, those selected from alkylene diamines, heteroalkylene diamines,arylene diamines, aralkylene diamines, or alkylene-aralkylene diamines.The diamine has only two amino groups so that the resultingpolydiorganosiloxane polyoxamides are linear block copolymers that areoften elastomeric, molten at elevated temperatures, and soluble in somecommon organic solvents. The diamine is free of a polyamine having morethan two primary or secondary amino groups. Tertiary amines that do notreact with the precursor of Formula II can be present. Additionally, thediamine is free of any carbonylamino group. That is, the diamine is notan amide.

Exemplary polyoxyalkylene diamines (i.e., G is a heteroalkylene with theheteroatom being oxygen) include, but are not limited to, thosecommercially available from Huntsman, The Woodlands, Tex. under thetrade designation JEFFAMINE D-230 (i.e., polyoxypropropylene diaminehaving an average molecular weight of about 230 g/mole), JEFFAMINE D-400(i.e., polyoxypropylene diamine having an average molecular weight ofabout 400 g/mole), JEFFAMINE D-2000 (i.e., polyoxypropylene diaminehaving an average molecular weight of about 2,000 g/mole), JEFFAMINEHK-511 (i.e., polyetherdiamine with both oxyethylene and oxypropylenegroups and having an average molecular weight of about 220 g/mole),JEFFAMINE ED-2003 (i.e., polypropylene oxide capped polyethylene glycolhaving an average molecular weight of about 2,000 g/mole), and JEFFAMINEEDR-148 (i.e., triethyleneglycol diamine).

Exemplary alkylene diamines (i.e., G is a alkylene) include, but are notlimited to, ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, 2-methylpentamethylene 1,5-diamine (i.e.,commercially available from DuPont, Wilmington, Del. under the tradedesignation DYTEK A), 1,3-pentane diamine (commercially available fromDuPont under the trade designation DYTEK EP), 1,4-cyclohexane diamine,1,2-cyclohexane diamine (commercially available from DuPont under thetrade designation DHC-99), 4,4′-bis(aminocyclohexyl)methane, and3-aminomethyl-3,5,5-trimethylcyclohexylamine.

Exemplary arylene diamines (i.e., G is an arylene such as phenylene)include, but are not limited to, m-phenylene diamine, o-phenylenediamine, and p-phenylene diamine. Exemplary aralkylene diamines (i.e., Gis an aralkylene such as alkylene-phenyl) include, but are not limitedto 4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e.,G is an alkylene-aralkylene such as alkylene-phenylene-alkylene)include, but are not limited to, 4-aminomethyl-benzylamine,3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.

The precursor of Formula II in Reaction Scheme A has at least onepolydiorganosiloxane segment and at least two oxalylamino groups. GroupR¹, group Y, subscript n, and subscript p are the same as described forFormula I. Each group R² is independently an alkyl, haloalkyl, aryl, oraryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl. Theprecursor of Formula II can include a single compound (i.e., all thecompounds have the same value of p and n) or can include a plurality ofcompounds (i.e., the compounds have different values for p, differentvalues for n, or different values for both p and n). Precursors withdifferent n values have siloxane chains of different length. Precursorshaving a p value of at least 2 are chain extended.

In some embodiments, the precursor is a mixture of a first compound ofFormula II with subscript p equal to 1 and a second compound of FormulaII with subscript p equal to at least 2. The first compound can includea plurality of different compounds with different values of n. Thesecond compound can include a plurality of compounds with differentvalues of p, different values of n, or different values of both p and n.Mixtures can include at least 50 weight percent of the first compound ofFormula II (i.e., p is equal to 1) and no greater than 50 weight percentof the second compound of Formula II (i.e., p is equal to at least 2)based on the sum of the weight of the first and second compounds in themixture. In some mixtures, the first compound is present in an amount ofat least 55 weight percent, at least 60 weight percent, at least 65weight percent, at least 70 weight percent, at least 75 weight percent,at least 80 weight percent, at least 85 weight percent, at least 90weight percent, at least 95 weight percent, or at least 98 weightpercent based on the total amount of the compounds of Formula II. Themixtures often contain no greater than 50 weight percent, no greaterthan 45 weight percent, no greater than 40 weight percent, no greaterthan 35 weight percent, no greater than 30 weight percent, no greaterthan 25 weight percent, no greater than 20 weight percent, no greaterthan 15 weight percent, no greater than 10 weight percent, no greaterthan 5 weight percent, or no greater than 2 weight percent of the secondcompound.

Different amounts of the chain-extended precursor of Formula II in themixture can affect the final properties of the elastomeric material ofFormula I. That is, the amount of the second compound of Formula II(i.e., p equal to at least 2) can be varied advantageously to provideelastomeric materials with a range of properties. For example, a higheramount of the second compound of Formula II can alter the melt rheology(e.g., the elastomeric material can flow easier when present as a melt),alter the softness of the elastomeric material, lower the modulus of theelastomeric material, or a combination thereof.

Reaction Scheme A can be conducted using a plurality of precursors ofFormula II, a plurality of diamines, or a combination thereof. Aplurality of precursors having different average molecular weights canbe combined under reaction conditions with a single diamine or withmultiple diamines. For example, the precursor of Formula II may includea mixture of materials with different values of n, different values ofp, or different values of both n and p. The multiple diamines caninclude, for example, a first diamine that is an organic diamine and asecond diamine that is a polydiorganosiloxane diamine. Likewise, asingle precursor can be combined under reaction conditions with multiplediamines.

The molar ratio of the precursor of Formula II to the diamine is oftenabout 1:1. For example, the molar ratio is often less than or equal to1:0.80, less than or equal to 1:0.85, less than or equal to 1:0.90, lessthan or equal to 1:0.95, or less than or equal to 1:1. The molar ratiois often greater than or equal to 1:1.05, greater than or equal to1:1.10, or greater than or equal to 1:1.15. For example, the molar ratiocan be in the range of 1:0.80 to 1:1.20, in the range of 1:0.80 to1:1.15, in the range of 1:0.80 to 1:1.10, in the range of 1:0.80 to1:1.05, in the range of 1:0.90 to 1:1.10, or in the range of 1:0.95 to1:1.05. Varying the molar ratio can be used, for example, to alter theoverall molecular weight, which can effect the rheology of the resultingcopolymers. Additionally, varying the molar ratio can be used to provideoxalylamino-containing end groups or amino end groups, depending uponwhich reactant is present in molar excess.

The condensation reaction of the precursor of Formula II with thediamine (i.e., Reaction Scheme A) are often conducted at roomtemperature or at elevated temperatures such as at temperatures up toabout 250° C. For example, the reaction often can be conducted at roomtemperature or at temperatures up to about 100° C. In other examples,the reaction can be conducted at a temperature of at least 100° C., atleast 120° C., or at least 150° C. For example, the reaction temperatureis often in the range of 100° C. to 220° C., in the range of 120° C. to220° C., or in the range of 150° C. to 200° C. The condensation reactionis often complete in less than 1 hour, in less than 2 hours, in lessthan 4 hours, in less than 8 hours, or in less than 12 hours.

Reaction Scheme A can occur in the presence or absence of a solvent.Suitable solvents usually do not react with any of the reactants orproducts of the reactions. Additionally, suitable solvents are usuallycapable of maintaining all the reactants and all of the products insolution throughout the polymerization process. Exemplary solventsinclude, but are not limited to, toluene, tetrahydrofuran,dichloromethane, aliphatic hydrocarbons (e.g., alkanes such as hexane),or mixtures thereof.

Any solvent that is present can be stripped from the resultingpolydiorganosiloxane polyoxamide at the completion of the reaction.Solvents that can be removed under the same conditions used to removethe alcohol by-product are often preferred. The stripping process isoften conducted at a temperature of at least 100° C., at least 125° C.,or at least 150° C. The stripping process is typically at a temperatureless than 300° C., less than 250° C., or less than 225° C.

Conducting Reaction Scheme A in the absence of a solvent can bedesirable because only the volatile by-product, R²OH, needs to beremoved at the conclusion of the reaction. Additionally, a solvent thatis not compatible with both reactants and the product can result inincomplete reaction and a low degree of polymerization.

Any suitable reactor or process can be used to prepare the copolymericmaterial according to Reaction Scheme A. The reaction can be conductedusing a batch process, semi-batch process, or a continuous process.Exemplary batch processes can be conducted in a reaction vessel equippedwith a mechanical stirrer such as a Brabender mixer, provided theproduct of the reaction is in a molten state has a sufficiently lowviscosity to be drained from the reactor. Exemplary semi-batch processcan be conducted in a continuously stirred tube, tank, or fluidized bed.Exemplary continuous processes can be conducted in a single screw ortwin screw extruder such as a wiped surface counter-rotating orco-rotating twin screw extruder.

In many processes, the components are metered and then mixed together toform a reaction mixture. The components can be metered volumetrically orgravimetrically using, for example, a gear, piston or progressing cavitypump. The components can be mixed using any known static or dynamicmethod such as, for example, static mixers, or compounding mixers suchas single or multiple screw extruders. The reaction mixture can then beformed, poured, pumped, coated, injection molded, sprayed, sputtered,atomized, stranded or sheeted, and partially or completely polymerized.The partially or completely polymerized material can then optionally beconverted to a particle, droplet, pellet, sphere, strand, ribbon, rod,tube, film, sheet, coextruded film, web, non-woven, microreplicatedstructure, or other continuous or discrete shape, prior to thetransformation to solid polymer. Any of these steps can be conducted inthe presence or absence of applied heat. In one exemplary process, thecomponents can be metered using a gear pump, mixed using a static mixer,and injected into a mold prior to solidification of the polymerizingmaterial.

The polydiorganosiloxane-containing precursor of Formula II in ReactionScheme A can be prepared by any known method. In some embodiments, thisprecursor is prepared according to Reaction Scheme B.

A polydiorganosiloxane diamine of Formula III (p moles) is reacted witha molar excess of an oxalate of Formula IV (greater than p+1 moles)under an inert atmosphere to produce the polydiorganosiloxane-containingprecursor of Formula II and R²—OH by-product. In this reaction, R¹, Y,n, and p are the same as previously described for Formula I. Each R² inFormula IV is independently an alkyl, haloalkyl, aryl, or arylsubstituted with an alkyl, alkoxy, halo, or alkoxycarbonyl. Thepreparation of the precursor of Formula II according to Reaction SchemeB is further described in copending patent application with AttorneyDocket No. 61369US002 filed on the same day as the present application,incorporated herein by reference in its entirety.

The polydiorganosiloxane diamine of Formula III in Reaction Scheme B canbe prepared by any known method and can have any suitable molecularweight, such as an average molecular weight in the range of 700 to150,000 g/mole. Suitable polydiorganosiloxane diamines and methods ofmaking the polydiorganosiloxane diamines are described, for example, inU.S. Pat. No. 3,890,269 (Martin), U.S. Pat. No. 4,661,577 (Jo Lane etal.), U.S. Pat. No. 5,026,890 (Webb et al.), U.S. Pat. No. 5,276,122(Aoki et al.), U.S. Pat. No. 5,214,119 (Leir et al.), U.S. Pat. No.5,461,134 (Leir et al.), U.S. Pat. No. 5,512,650 (Leir et al.), and U.S.Pat. No. 6,355,759 (Sherman et al.), incorporated herein by reference intheir entirety. Some polydiorganosiloxane diamines are commerciallyavailable, for example, from Shin Etsu Silicones of America, Inc.,Torrance, Calif. and from Gelest Inc., Morrisville, Pa.

A polydiorganosiloxane diamine having a molecular weight greater than2,000 g/mole or greater than 5,000 g/mole can be prepared using themethods described in U.S. Pat. No. 5,214,119 (Leir et al.), U.S. Pat.No. 5,461,134 (Leir et al.), and U.S. Pat. No. 5,512,650 (Leir et al.).One of the described methods involves combining under reactionconditions and under an inert atmosphere (a) an amine functional endblocker of the following formula

where Y and R¹ are the same as defined for Formula I; (b) sufficientcyclic siloxane to react with the amine functional end blocker to form apolydiorganosiloxane diamine having a molecular weight less than 2,000g/mole; and (c) an anhydrous aminoalkyl silanolate catalyst of thefollowing formula

where Y and R¹ are the same as defined in Formula I and M⁺ is a sodiumion, potassium ion, cesium ion, rubidium ion, or tetramethylammoniumion. The reaction is continued until substantially all of the aminefunctional end blocker is consumed and then additional cyclic siloxaneis added to increase the molecular weight. The additional cyclicsiloxane is often added slowly (e.g., drop wise). The reactiontemperature is often conducted in the range of 80° C. to 90° C. with areaction time of 5 to 7 hours. The resulting polydiorganosiloxanediamine can be of high purity (e.g., less than 2 weight percent, lessthan 1.5 weight percent, less than 1 weight percent, less than 0.5weight percent, less than 0.1 weight percent, less than 0.05 weightpercent, or less than 0.01 weight percent silanol impurities). Alteringthe ratio of the amine end functional blocker to the cyclic siloxane canbe used to vary the molecular weight of the resultingpolydiorganosiloxane diamine of Formula III.

Another method of preparing the polydiorganosiloxane diamine of FormulaIII includes combining under reaction conditions and under an inertenvironment (a) an amine functional end blocker of the following formula

where R¹ and Y are the same as described for Formula I and where thesubscript x is equal to an integer of 1 to 150; (b) sufficient cyclicsiloxane to obtain a polydiorganosiloxane diamine having an averagemolecular weight greater than the average molecular weight of the aminefunctional end blocker; and (c) a catalyst selected from cesiumhydroxide, cesium silanolate, rubidium silanolate, cesiumpolysiloxanolate, rubidium polysiloxanolate, and mixtures thereof. Thereaction is continued until substantially all of the amine functionalend blocker is consumed. This method is further described in U.S. Pat.No. 6,355,759 B1 (Sherman et al.). This procedure can be used to prepareany molecular weight of the polydiorganosiloxane diamine.

Yet another method of preparing the polydiorganosiloxane diamine ofFormula III is described in U.S. Pat. No. 6,531,620 B2 (Brader et al.).In this method, a cyclic silazane is reacted with a siloxane materialhaving hydroxy end groups as shown in the following reaction.

The groups R¹ and Y are the same as described for Formula I. Thesubscript m is an integer greater than 1.

Examples of polydiorganosiloxane diamines include, but are not limitedto, polydimethylsiloxane diamine, polydiphenylsiloxane diamine,polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxanediamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine,polyvinylmethylsiloxane diamine, poly(5-hexenyl)methylsiloxane diamine,and mixtures thereof.

In Reaction Scheme B, an oxalate of Formula IV is reacted with thepolydiorganosiloxane diamine of Formula III under an inert atmosphere.The two R² groups in the oxalate of Formula IV can be the same ordifferent. In some methods, the two R² groups are different and havedifferent reactivity with the polydiorganosiloxane diamine of FormulaIII in Reaction Scheme B.

Group R² can be an alkyl, haloalkyl, aryl, or aryl substituted with analkyl, alkoxy, halo, or alkoxycarbonyl. Suitable alkyl and haloalkylgroups for R² often have 1 to 10, 1 to 6, or 1 to 4 carbon atoms.Although tertiary alkyl (e.g., tert-butyl) and haloalkyl groups can beused, there is often a primary or secondary carbon atom attacheddirectly (i.e., bonded) to the adjacent oxy group. Exemplary alkylgroups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, andiso-butyl. Exemplary haloalkyl groups include chloroalkyl groups andfluoroalkyl groups in which some, but not all, of the hydrogen atoms onthe corresponding alkyl group are replaced with halo atoms. For example,the chloroalkyl or a fluoroalkyl groups can be chloromethyl,2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl, 4-chlorobutyl,fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl,4-fluorobutyl, and the like. Suitable aryl groups for R² include thosehaving 6 to 12 carbon atoms such as, for example, phenyl. An aryl groupcan be unsubstituted or substituted with an alkyl (e.g., an alkyl having1 to 4 carbon atoms such as methyl, ethyl, or n-propyl), an alkoxy(e.g., an alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, orpropoxy), halo (e.g., chloro, bromo, or fluoro), or alkoxycarbonyl(e.g., an alkoxycarbonyl having 2 to 5 carbon atoms such asmethoxycarbonyl, ethoxycarbonyl, or propoxycarbonyl).

The oxalates of Formula IV in Reaction Scheme B can be prepared, forexample, by reaction of an alcohol of formula R²—OH with oxalyldichloride. Commercially available oxalates of Formula IV (e.g., fromSigma-Aldrich, Milwaukee, Wis. and from VWR International, Bristol,Conn.) include, but are not limited to, dimethyl oxalate, diethyloxalate, di-n-butyl oxalate, di-tert-butyl oxalate, bis(phenyl)oxalate,bis(pentafluorophenyl) oxalate,1-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl) oxalate, and bis(2,4,6-trichlorophenyl) oxalate.

A molar excess of the oxalate is used in Reaction Scheme B. That is, themolar ratio of oxalate to polydiorganosiloxane diamine is greater thanthe stoichiometric molar ratio, which is (p+1): p. The molar ratio isoften greater than 2:1, greater than 3:1, greater than 4:1, or greaterthan 6:1. The condensation reaction typically occurs under an inertatmosphere and at room temperature upon mixing of the components.

The condensation reaction used to produce the precursor of Formula II(i.e., Reaction Scheme B) can occur in the presence or absence of asolvent. In some methods, no solvent or only a small amount of solventis included in the reaction mixture. In other methods, a solvent may beincluded such as, for example, toluene, tetrahydrofuran,dichloromethane, or aliphatic hydrocarbons (e.g., alkanes such ashexane).

Removal of excess oxalate from the precursor of Formula II prior toreaction with the diamine in Reaction Scheme A tends to favor formationof an optically clear polydiorganosiloxane polyoxamide. The excessoxalate can typically be removed from the precursor using a strippingprocess. For example, the reacted mixture (i.e., the product or productsof the condensation reaction according to Reaction Scheme B) can beheated to a temperature up to 150° C., up to 175° C., up to 200° C., upto 225° C., or up to 250° C. to volatilize the excess oxalate. A vacuumcan be pulled to lower the temperature that is needed for removal of theexcess oxalate. The precursor compounds of Formula II tend to undergominimal or no apparent degradation at temperatures in the range of 200°C. to 250° C. or higher. Any other known methods of removing the excessoxalate can be used.

The by-product of the condensation reaction shown in Reaction Scheme Bis an alcohol (i.e., R²—OH is an alcohol). Group R² is often limited toan alkyl having 1 to 4 carbon atoms, a haloalkyl having 1 to 4 carbonatoms, or an aryl such as phenyl that form an alcohol that can bereadily removed (e.g., vaporized) by heating at temperatures no greaterthan about 250° C. Such an alcohol can be removed when the reactedmixture is heated to a temperature sufficient to remove the excessoxalate of Formula IV.

The foregoing describes the invention in terms of embodiments foreseenby the inventor for which an enabling description was available,notwithstanding that insubstantial modifications of the invention, notpresently foreseen, may nonetheless represent equivalents thereto.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, and the like in the examples and are by weight,unless noted otherwise. Solvents and other reagents used were obtainedfrom Sigma-Aldrich Chemical Company; Milwaukee, Wis. unless otherwisenoted.

Table of Abbreviations Abbreviation or Trade Designation Description 5KPDMS A polydimethylsiloxane diamine with an average molecular diamineweight of about 5,000 g/mole that was prepared as described in U.S. Pat.No. 5,214,119. 14K PDMS Polydimethylsiloxane diamine with an approximatediamine molecular weight of 14,000 g/mole that was prepared as describedin U.S. Pat. No. 6,355,759. 33K PDMS Polydimethylsiloxane diamine withan approximate diamine molecular weight of 33,000 g/mole that wasprepared as described in U.S. Pat. No. 6,355,759. DMS-A12Polydimethylsiloxane diamine with an approximate molecular weight of 900g/mole that was purchased from Gelest, Inc., Morrisville, PA DMS-A15Polydimethylsiloxane diamine with an approximate molecular weight of2,500 g/mole that was purchased from Gelest, Inc., Morrisville, PA THFTetrahydrofuran EDA Ethylene diamine BDA 1,4-butane diamine HDA1,6-hexane diamine XDA m-xylene diamine DHC-99 1,2-cyclohexane diamine,DuPont, Wilmington, DE H12-MDA 4,4′-bis(aminocyclohexyl)methane,Aldrich, Milwaukee, WI EDR-148 Triethyleneglycol diamine, Huntsman, TheWoodlands, TX DYTEK A 2-methylpentane 1,5-diamine, DuPont, Wilmington,DE

Test Methods Hardness Testing

Shore A Hardness was measured according to ASTM D2240-5 Standard TestMethod for Rubber Property-Durometer Hardness. This test method is basedon the penetration of a specific type of indentor when forced into thematerial under specified conditions. The indentation hardness isinversely related to the penetration and is dependent on the elasticmodulus and viscoelastic behavior of the material.

Titration Method to Determine Equivalent Weight

Approximately 10 grams (precisely weighed) of the precursor compound ofFormula II was added to a jar. Approximately 50 grams THF solvent (notprecisely weighed) was added. The contents were mixed using a magneticstir bar mix until the mixture was homogeneous. The theoreticalequivalent weight of precursor was calculated and then an amount ofN-hexylamine (precisely weighed) in the range of 3 to 4 times thisnumber of equivalents was added. The reaction mixture was stirred for aminimum of 4 hours. Bromophenol blue (10-20 drops) was added and thecontents were mixed until homogeneous. The mixture was titrated to ayellow endpoint with 1.0N (or 0.1N) hydrochloric acid. The number ofequivalents of precursor was equal to the number of equivalents ofN-hexylamine added to the sample minus the number of equivalents ofhydrochloric acid added during titration. The equivalent weight(grams/equivalent) was equal to the sample weight of the precursordivided by the number of equivalents of the precursor.

Color, Haze, and Luminous Transmittance Measurement

The luminous transmittance and haze of the samples were measuredaccording to the American Society for Testing and Materials (ASTM) TestMethod D 1003-95 (“Standard Test for Haze and Luminous Transmittance ofTransparent Plastic”) using a TCS Plus Spectrophotometer fromBYK-Gardner Inc., Silver Springs, Md. Color measurements were made usingthe same instrument, following the CIE (French abbreviation forCommission of Lighting) established international color scale of L*, a*,b*.

Preparative Example 1

Diethyl oxalate (241.10 grams) was placed in a 3 liter, 3-neck resinflask equipped with a mechanical stirrer, heating mantle, nitrogen inlettube (with stopcock), and an outlet tube. The flask was purged withnitrogen for 15 minutes and 5K PDMS diamine (2,028.40 grams, molecularweight equal to 4,918 g/mole) was added slowly with stirring. After 8hours at room temperature, the reaction flask was fitted with adistillation adaptor and receiver. The contents were stirred and heatedto 150° C. under vacuum (133 Pascals, 1 Torr) for 4 hours, until nofurther distillate was able to be collected. The remaining liquid wascooled to room temperature to provide 2,573 grams of a precursor ofFormula II. Gas chromatographic analysis of the clear, mobile liquidshowed that no detectable level of diethyl oxalate remained. Molecularweight was determined using ¹H NMR (molecular weight equal to 5,477grams/mole) and by titration (equivalent weights of 2,722grams/equivalent and 2,721 grams/equivalent for two samples titrated).

Preparative Example 2

Diethyl oxalate (326.00 grams) was placed in a 2 liter, 3-neck resinflask equipped with a mechanical stirrer, heating mantle, nitrogen inlettube (with stopcock), and an outlet tube. The flask was purged withnitrogen for 15 minutes and then, with vigorous stirring, DMS-A12(497.50 grams) was added dropwise. This reaction mixture was stirred forapproximately one hour at room temperature and then for 75 minutes at80° C. The reaction flask was fitted with a distillation adaptor andreceiver. The reaction mixture was heated to 120° C. under vacuum (133Pascals, 1 Torr) for 2 hours, until no further distillate was able to becollected. The reaction mixture was cooled to room temperature toprovide a precursor of Formula II. Gas chromatographic analysis of theclear, mobile liquid showed that no detectable level of diethyl oxalateremained. The ester equivalent weight was determined using ¹H NMR(equivalent weight equal to 923 grams/equivalent) and by titration(equivalent weight equal to 910 grams/equivalent).

Preparative Example 3

A sample of DMS-A12 (500.00 grams) was placed in a 2 liter, 3-neck resinflask equipped with a mechanical stirrer, heating mantle, nitrogen inlettube (with stopcock), and an outlet tube. The flask was purged withnitrogen for 15 minutes and then, with vigorous stirring, diethyloxalate (324.76 grams) was added dropwise. This reaction mixture wasstirred for approximately one hour at room temperature and then for 75minutes at 80° C. The reaction flask was fitted with a distillationadaptor and receiver. The reaction mixture was heated under vacuum (133Pascals, 1 Torr) for 2 hours at 120° C. and then 30 minutes at 130° C.,until no further distillate was able to be collected. The reactionmixture was cooled to room temperature to provide a precursor of FormulaII. Gas chromatographic analysis of the clear, mobile liquid showed thatno detectable level of diethyl oxalate remained. The ester equivalentweight was determined using ¹H NMR (equivalent weight equal to 1,293grams/equivalent).

Preparative Example 4

A sample of DMS-A15 (500.00 grams) was placed in a 2 liter, 3-neck resinflask equipped with a mechanical stirrer, heating mantle, nitrogen inlettube (with stopcock), and an outlet tube. The flask was purged withnitrogen for 15 minutes and then, with vigorous stirring, diethyloxalate (116.92 grams) was added dropwise. This reaction mixture wasstirred for approximately one hour at room temperature and then for 75minutes at 80° C. The reaction flask was fitted with a distillationadaptor and receiver. The reaction mixture was heated under vacuum (133Pascals, 1 Torr) for 2 hours at 120° C. and then 30 minutes at 130° C.,until no further distillate was able to be collected. The reactionmixture was cooled to room temperature to provide a precursor of FormulaII. Gas chromatographic analysis of the clear, mobile liquid showed thatno detectable level of diethyl oxalate remained. The ester equivalentweight was determined using ¹H NMR (equivalent weight equal to 1,788grams/equivalent) and by titration (equivalent weight equal to 1,753grams/equivalent).

Preparative Example 5

A sample of 14K PDMS diamine (830.00 grams, molecular weight 14,460g/mole) was place in a 2 liter, 3-neck resin flask equipped with amechanical stirrer, heating mantle, nitrogen inlet tube (with stopcock),and an outlet tube. The flask was purged with nitrogen for 15 minutesand then, with vigorous stirring, diethyl oxalate (33.56 grams) wasadded dropwise. This reaction mixture was stirred for approximately onehour at room temperature and then for 75 minutes at 80° C. The reactionflask was fitted with a distillation adaptor and receiver. The reactionmixture was heated under vacuum (133 Pascals, 1 Torr) for 2 hours at120° C. and then 30 minutes at 130° C., until no further distillate wasable to be collected. The reaction mixture was cooled to roomtemperature to provide a precursor of Formula II. Gas chromatographicanalysis of the clear, mobile liquid showed that no detectable level ofdiethyl oxalate remained. The ester equivalent weight was determinedusing ¹H NMR (equivalent weight equal to 7,916 grams/equivalent) and bytitration (equivalent weight equal to 8,272 grams/equivalent).

Example 1

The precursor of Preparative Example 1 (793.20 grams) was placed in a 3liter, 3-neck resin flask equipped with a mechanical stirrer, heatingmantle, nitrogen inlet tube (with stopcock), and an outlet tube. Theflask was purged with nitrogen for 15 minutes and hexane diamine (17.48grams) was added. The mixture was mechanically stirred and heated to150° C. under a nitrogen atmosphere for 3.5 hours. The viscous moltenproduct was poured into a glass tray and allowed to cool. Thepolydimethylsiloxane polyoxamide was a clear, elastomeric slab having aShore A hardness of 59.

The color, haze, and luminous transmittance properties were measured ona 24 micron thick melt-pressed sample. The luminous transmittanceexceeded 91% for the wavelengths between 400 nm and 700 nm. The C2*percent haze value was 1.7 percent, and the A2* percent haze value was1.6 percent. The L*, a*, b* values were respectively 97.15, 0.03, and0.52.

Example 2

The precursor of Preparative Example 1 (100.00 grams) was placed in a16-ounce wide mouth jar. EDA (1.0243 grams) was added. The jar wassealed and the mixture was rapidly agitated until the contents becametoo viscous to flow. After sitting overnight at ambient temperature, thesolid product was dissolved in THF (200 grams). A film was cast bypouring the solution into a Petri dish and then by slowly evaporatingthe THF overnight at ambient temperature. The polydimethylsiloxanepolyoxamide was a clear elastomeric film having a Shore A hardness of55.

Example 3

The precursor of Preparative Example 1 (100.00 grams) was placed in a16-ounce wide mouth jar. An aliquot of BDA (1.5025 grams) was added. Thejar was sealed and the mixture was rapidly agitated until the contentsbecame too viscous to flow. The jar was placed on a roller millovernight at ambient temperature. The solid product was dissolved in THF(200 grams). A film was cast by pouring the solution into a Petri dishand then by slowly evaporating the THF overnight at ambient temperature.The polydimethylsiloxane polyoxamide was a clear elastomeric film havinga Shore A hardness of 54.

Example 4

The precursor of Preparative Example 1 (100.00 grams) and HDA (2.0013grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated. The jar was place on a roller mill rollerovernight at ambient temperature. The solid product was dissolved in THF(200 grams). A film was cast by pouring the solution into a Petri dishand then by slowly evaporating the THF overnight at ambient temperature.The polydimethylsiloxane polyoxamide was a clear elastomeric film havinga Shore A hardness of 51.

Example 5

The precursor of Preparative Example 2 (100.00 grams) and EDA (3.33grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, flexible film (e.g., thefilm could be bent without breaking) having a Shore A hardness of 88.

Example 6

The precursor of Preparative Example 2 (100.00 grams) and XDA (7.55grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, flexible film (e.g., thefilm could be bent without breaking) having a Shore A hardness of 88.

Example 7

The precursor of Preparative Example 2 (10.00 grams) and EDR-148 diamine(0.81 grams) were weighed into an 8-dram vial. The vial was sealed andthe mixture was rapidly agitated until the contents became too viscousto flow. The vial was placed on a roller mill overnight at ambienttemperature. The product was heated to 130° C. and cast as a film withina glass Petri dish. The polydimethylsiloxane polyoxamide was a clearelastomeric film having a Shore A hardness of 85.

Example 8

The precursor of Preparative Example 2 (10.00 grams) and DYTEK A diamine(0.6380 grams) were weighed into an 8-dram vial. The vial was sealed andthe mixture was rapidly agitated until the contents became too viscousto flow. The vial was placed on a roller mill overnight at ambienttemperature. The product was heated to 130° C. and cast into a glassPetri dish. The polydimethylsiloxane polyoxamide was a clear elastomericfilm having a Shore A hardness of 85.

Example 9

The precursor of Preparative Example 2 (10.00 grams) and DHC-99 (0.6274grams) were weighed into an 8-dram vial. The vial was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The product was heated to 170° C. for one hour and then cast as afilm within a glass Petri dish. The polydimethylsiloxane polyoxamide wasa clear elastomeric film having a Shore A hardness of 76.

Example 10

The precursor of Preparative Example 2 (10.00 grams) and H12-MDA (1.1751grams) were weighed into a vial. The vial was sealed and the mixture wasrapidly agitated until the contents became too viscous to flow. Theproduct was heated to 170° C. for one hour and then cast as a filmwithin a glass Petri dish. The polydimethylsiloxane polyoxamide was aclear elastomeric film having a Shore A hardness of 81.

Example 11

The precursor of Preparative Example 3 (100.00 grams) and EDA (2.34grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, flexible film (e.g., thefilm could be bent without breaking) having a Shore A hardness of 78.

Example 12

The precursor of Preparative Example 3 (100.00 grams) and XDA (5.32grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, flexible film (e.g., thefilm could be bent without breaking) having a Shore A hardness of 78.

Example 13

The precursor of Preparative Example 4 (100.00 grams) and EDA (1.73grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, leathery film having aShore A hardness of 75.

Example 14

The precursor of Preparative Example 4 (100.00 grams) and XDA (3.92grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, leathery film having aShore A hardness of 72.

Example 15

The precursor of Preparative Example 1 (100.00 grams) and XDA (2.32grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear elastomeric film having aShore A hardness of 60.

Example 16

The precursor of Preparative Example 5 (98.13 grams) and EDA (0.36grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was stirred agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, elastomeric film having aShore A hardness of 38.

Example 17

The precursor of Preparative Example 5 (100.00 grams) and XDA (0.83grams) were weighed into a 16-ounce jar. The jar was sealed and themixture was rapidly agitated until the contents became too viscous toflow. The jar was placed on a roller mill overnight at ambienttemperature. The solid product was dissolved in THF (200 grams). A filmwas cast by pouring the solution into a Petri dish and then by slowlyevaporating the THF overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear, elastomeric film having aShore A hardness of 33.

Example 18

The precursor of Preparative Example 1 (150.00 grams) was charged into a2 liter, 3-neck resin flask equipped with a mechanical stirrer, heatingmantle, nitrogen inlet tube (with stopcock), and an outlet tube. Withvigorous stirring at ambient temperature, BDA (2.5767 grams) was addeddropwise. This reaction mixture was stirred at ambient temperature untilthe viscosity became too high to mix, and then the mixture was heated to175° C. with stirring for one hour. The viscous, molten product was castas a slab by pouring the mixture into a glass baking dish and cooling toroom temperature. The clear elastomeric slab had a Shore A hardness of61.

Example 19

The precursor of Preparative Example 2 (10.00 grams) and hexane (16.10grams) were weighed into a 4-ounce jar and mixed until homogeneous. Analiquot of XDA (0.7559 grams) was added and the mixture was stirredrapidly for about 2 minutes. A film was cast by pouring the solutioninto a Petri dish and then by slowly evaporating the hexane overnight.The polydimethylsiloxane polyoxamide was a clear, flexible film (e.g.,the film could be bent without breaking) having a Shore A hardness of79.

Example 20

A sample of 33K PDMS diamine (15.00 grams) was place in a reactionvessel. The PDMS diamine was degassed by heating to 100° C. under vacuumfor about 30 minutes and then cooled to ambient temp. Toluene (138.00grams) was added to the PDMS diamine and the resulting mixture was mixeduntil homogeneous. Di(trifluorethyl) oxalate (0.4666 gram) was added andthe mixture was stirred for 90 minutes at ambient temp. A homogeneousmixture of HDA (0.1615 gram) and toluene (3.00 grams) was added and theresulting mixture was agitated on a roller mill. After 4 days, thecontents had solidified to a clear gel. Isopropyl alcohol (16.20 grams)was added and the mixture was heated in a 55° C. oven until a fluidsolution was obtained, and then poured into a Petri dish. The solventswere allowed to evaporate slowly overnight at ambient temperature. Thepolydimethylsiloxane polyoxamide was a clear elastomeric film having aShore A hardness of 14.

Example 21

Precursor of Preparative Example 1 (equivalent weight of 3,399) wasreacted with EDA, using a continuous, solventless, ambient temperatureprocess, which generated solid polymeric material in several minutes.Gear pumps were used to continuously meter co-reactant feed streams, andstatic mixers were utilized to accomplish mixing. The mixed feed streamwas dispensed into receptacles such as jars, trays or molds, prior toformation of solid polymer product. Two gear pumps, each mounted on apump cart equipped with a drive motor, digital rpm readout, nitrogenpurged reservoir tank (EDA only) and flexible high density polyethylenetubing lines (0.635 centimeter outer diameter for precursor and 0.317centimeter outer diameter for EDA), were used to deliver a continuousprecursor feed stream of 34.74 grams/minute, and an EDA feed stream of0.31 gram/minute, at a back pressure greater than 76 kiloPascals. Duringflow calibration, each feed line was equipped with a flow restrictorneedle valve and back pressure gauge. The two co-reactant streams werecombined in a stainless T-shaped feedblock, and the resulting blend wasmixed via static mixer (20.3 centimeter length, 0.95 centimeter diameterand 24 elements). The mixed stream was dispensed into jars and otherreceptacles. Solid polymeric material was formed within several minutes(e.g., 2 minutes). Titration of reaction product for these co-reactantsconfirmed that about 99 percent reaction conversion was achieved afterone hour or less, and that additional curing occurred at ambienttemperature.

Example 22

A sample of the polymer prepared in Example 1 (25 grams) was cut intorectangular strips. These strips were loaded into a hot glue gun thatwas obtained from 3M under the trade designation POLYGUN TC (#B93745,150 watts, 60 CPS). The gun was plugged in and allowed to heat-up forabout 10 minutes. The temperature inside the barrel was 200° C. Themolten polymer was extruded from the gun as a thin bead onto one end ofa 10 centimeter by 10 centimeter (4 inch×4 inch) glass coupon. Whilestill molten, a second glass coupon was pressed down firmly onto thebead, which caused it to spread out as a thin film between the twopieces of glass. This overlapping bond had an area of 10 centimeters by4 centimeters (4 inches×1.6 inches). A similar bond was formed betweentwo 18 centimeter by 7.6 centimeter (7 inches×3 inches) softwoodcoupons. The bond area of the wood was 7.6 centimeters by 8.25centimeters (3 inches×3.25 inches). These bonded panels were allowed tosit for several weeks, at which time it was attempted to pull themapart. Neither bond could be pulled apart by hand in the tensile mode.

1. A compound of Formula II:

wherein each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each R² isindependently an alkyl, haloalkyl, aryl, or aryl substituted with analkyl, alkoxy, halo, or alkoxycarbonyl; each Y is independently analkylene, aralkylene, or a combination thereof; each n is independentlyan integer of 0 to 1500; and p is an integer of 1 to
 10. 2. The compoundof claim 1, wherein R¹ is methyl.
 3. The compound of claim 1, wherein atleast 50 percent of the R¹ groups are methyl.
 4. The compound of claim1, wherein each R² is an alkyl having 1 to 4 carbon atoms or a haloalkylhaving 1 to 4 carbon atoms, the alkyl or haloalkyl having a primarycarbon atom or secondary carbon atom bonded to the adjacent oxy group.5. The compound of claim 1, wherein each R² is a phenyl or a phenylsubstituted with an alkyl having 1 to 4 carbon atoms, with an alkoxyhaving 1 to 4 carbon atoms, with a halo, or with an alkoxycarbonylhaving 2 to 5 carbon atoms.
 6. The compound of claim 1, wherein each Yis an alkylene having 1 to 10 carbon atoms, phenylene bonded to analkylene having 1 to 10 carbon atoms, or phenylene bonded to a firstalkylene having 1 to 10 carbon atoms and to a second alkylene having 1to 10 carbon atoms.
 7. The compound of claim 1, wherein n is an integerof 0 to
 500. 8. The compound of claim 1, wherein p is an integer of 1 to4.
 9. A composition comprising: a) at least one first compound ofFormula IIa; and

b) at least one second compound of Formula II

wherein Formula IIa is the compound of Formula II wherein p=1, andwherein each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each R² isindependently an alkyl, haloalkyl, aryl, or aryl substituted with analkyl, alkoxy, halo, or alkoxycarbonyl; each Y is independently analkylene, aralkylene, or a combination thereof; each n is independentlyan integer of 0 to 1500; and p is an integer of 2 to
 10. 10. Thecomposition of claim 9, wherein R¹ is methyl.
 11. The composition ofclaim 9, wherein each R² is an alkyl having 1 to 4 carbon atoms or ahaloalkyl having 1 to 4 carbon atoms, the alkyl or haloalkyl having aprimary carbon atom or secondary carbon atom bonded to the adjacent oxygroup.
 12. The composition of claim 9, wherein each R² is a phenyl or aphenyl substituted with an alkyl having 1 to 4 carbon atoms, with analkoxy having 1 to 4 carbon atoms, with a halo, or with analkoxycarbonyl having 2 to 5 carbon atoms.
 13. The composition of claim9, wherein each Y is an alkylene having 1 to 10 carbon atoms, phenylenebonded to an alkylene having 1 to 10 carbon atoms, or phenylene bondedto a first alkylene having 1 to 10 carbon atoms and to a second alkylenehaving 1 to 10 carbon atoms.
 14. The composition of claim 9, wherein thecomposition comprises at least 50 weight percent of the first compoundof Formula II and no greater than 50 weight percent of the secondcompound of Formula III based on the sum of the weight of the first andsecond compounds in the mixture.
 15. A method of making a compound ofFormula II,

the method comprising mixing a polydiorganosiloxane diamine of FormulaIII

with a molar excess of an oxalate of Formula IV,

wherein each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each R² isindependently an alkyl, haloalkyl, aryl, or aryl substituted with analkyl, alkoxy, halo, or alkoxycarbonyl; each Y is independently analkylene, aralkylene, or a combination thereof n is independently aninteger of 0 to 1500; and p is an integer of 1 to
 10. 16. The method ofclaim 15, wherein each R² is an alkyl having 1 to 4 carbon atoms or ahaloalkyl having 1 to 4 carbon atoms, the alkyl or haloalkyl having aprimary carbon atom or secondary carbon atom bonded to the adjacent oxygroup.
 17. The method of claim 15, wherein each R² is a phenyl or aphenyl substituted with an alkyl having 1 to 4 carbon atoms, with analkoxy having 1 to 4 carbon atoms, with a halo, or with analkoxycarbonyl having 2 to 5 carbon atoms.
 18. The method of claim 15,further comprising removing the excess oxalate after reaction of thepolydiorganosiloxane diamine and the oxalate.
 19. The method of claim15, wherein the two R² groups of the oxalate of Formula IV aredifferent.
 20. The method of claim 15, wherein R¹ is methyl.